Calixarene acetamido derivatives, preparation and use thereof for extracting strontium

ABSTRACT

The invention concerns derivatives of calixarene having the formula:                    
     in which: 
     R 1  represents various hydrocarbon groups, 
     R 2  and R 3  represent an alkyl, cycloalkyl or aryl group or a group having the formula: O(CH 2 ) n [O(CH 2 ) p ] q  OR 4 , or form a heterocyclic group with the nitrogen atom, and, 
     n equals 6, 7 or 8. 
     These derivatives can be used for extracting strontium from aqueous solutions.

TECHNICAL FIELD

The subject of the present invention is new derivatives of calixarenescarrying amide groups, their method of preparation and their use toextract strontium.

These new calixarene derivatives may be used to extract strontiumpresent in aqueous solutions derived from reprocessing plants for spentnuclear fuel.

STATE OF PRIOR ART

The use of macrocyclic ligands such as calixarenes has already beenconsidered to extract metals from aqueous solutions. DocumentsWO94/12502 [1] and WO94/24138 [2] describe crown-calixarenes which canbe used for the selective extraction of caesium and actinides.

The extraction of caesium from aqueous solutions is of interest ascaesium releases heat which hampers the storage of nitric solutions offission products.

Strontium 90 is also an isotope giving major heat release, strontium andcaesium accounting for more than 90% of the heat released from solutionsof fission products.

Therefore, their removal from these solutions would facilitate thestorage of such solutions. Also, the removal of caesium, strontium andactinides may make it possible to declassify type B waste so that it canbe addressed to an existing surface storage rather than to a storagesite under geological formation.

Solutions of this type may for example be evaporator concentrates orsolutions generated by dismantling operations.

The subject of the present invention is precisely new derivatives ofcalixarenes.

DISCLOSURE OF THE INVENTION

The subject matter of the present invention is precisely new derivativesof calixarenes which lead to satisfactory extraction of strontium.

According to the invention, the new derivative of calixarene meets theformula:

in which:

R¹ represents a hydrogen atom, a hydroxyl, alkyl, alcoxy, aryl, aryloxy,arylalkyl, arylalcoxy, cycloalkyl or cycloalcoxy group, or a grouphaving the formula O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴represents a hydrogen atom or an alkyl group, n and p are whole numbersranging from 1 to 6, and q equals 0 or is a whole number from 1 to 6,

R² and R³, which may identical or different, represent an alkyl,cycloalkyl or aryl group or a group having the formula:O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴, n, p and q are such asdefined above, or

R² and R³, together with the nitrogen atom to which they are bound, forma heterocyclic group chosen from among the piperidyl, pyrrolidinyl,morpholinyl, thiomorpholinyl, tetrahydropyridyl, imidazolidinyl,indolinyl, tetrahydroquinolyl and perhydroindolyl groups, and

m is a whole number ranging from 6 to 8.

In this formula, the alkyl and alcoxy groups may be linear or branchedgroups, preferably with 1 to 12 carbon atoms. The aryl and aryloxygroups which may be used are monovalent groups derived from an aromaticor heterocyclic core through removal of one hydrogen atom from one ofthe carbon atoms of the cycle.

By way of example of such groups, mention may be made of the phenyl,naphtyl, pyridyl, thiophenyl and substituted phenyl groups.

For R¹ it is also possible to use arylalkyl and arylalcoxy groups inwhich the alkyl or alcoxy group preferably has from 1 to 12 carbonatoms.

As an example of such groups, the benzyloxy group and the benzyl groupmay be cited.

When R¹ represents the group of formula (II), R⁴ may be a hydrogen atomor a alkyl group preferably having from 1 to 12 carbon atoms.

According to the invention, R¹ is preferably an alkyl, alcoxy orarylalcoxy group, for example the tert-butyl group, the pentoxy oroctoxy group, or the benzyloxy group.

According to the invention, R² and R³ may be alkyl, cycloalkyl or arylgroups having from 1 to 12 carbon atoms.

Preferably, R² and R³ are alkyl groups, the ethyl group for example.

The calixarenes may comprise from 6 to 8 phenyl cycles and thederivative preferably comprises 6 or 8 phenyl cycles, that is to saythat m equals 6 or 8.

The calixarene derivatives of the invention may be prepared usingmethods that are easy to implement.

Therefore, if R¹ represents a hydrogen atom, an alkyl group or abenzyloxy group, the calixarene of formula (I) may be prepared in whichR² and R³ are such as defined above, using a method which comprises thereaction of a calixarene having the formula:

in which R¹ and m are as defined above, with a chloroacetamide havingthe formula:

in which R² and R³ are such as defined above.

If, in the calixarene of formula (I) described above, R¹ represents analcoxy group, this derivative of calixarene may be prepared using amethod which comprises the following steps:

a) the reaction of a calixarene of formula:

 in which m is such as defined above, with a chloroacetamide having theformula:

 in which R² and R³ are such as defined above, to obtain the derivativehaving the formula:

 in which R and R are such as defined above.

b) reaction of the derivative of formula (VI) with Pd(OH₂) to obtain thecalixarene having the formula:

c) reaction of the calixarene of formula VII with a halogenatedderivative of formula R⁵X in which R⁵ represents an alkyl group and X isa halogen atom, to obtain the calixarene derivative of formula (I) inwhich R¹ represents the alcoxy group OR⁵.

The calixarenes of formula (III) used as starting products for thepreparation of the derivatives of the invention may be prepared bycondensation reaction of p-benzyloxyphenol having the formula:

to obtain a mixture of calix[6]arene, calix[7]arene and calix[8]arene offormula (III), and separation of the calixarene of formula (III) inwhich m=6 or 8.

The calixarenes of formula (I) of the invention may be used to extractthe strontium present in an aqueous solution, in particular an acid orsaline solution derived from reprocessing plants for spent nuclear fuel.

The calixarenes of the invention which contain an acetamido group inwhich the amido group is a tertiary amide group (R1 and R2 being alkylgroups), are much more efficient and much more selective towardsstrontium than calixarenes which have a secondary amide group (R1=H,R2=alkyl) or a primary amide group (R1=R2=H).

In addition, the presence of the hydroxy, alcoxy, aryloxy, arylalcoxy orcycloalcoxy groups on the phenyl cores of calixarene makes them evenmore selective towards strontium. It has been observed that calixarenesusing alkyl groups do extract strontium but less so than sodium.

The method of extraction of the invention is intended in particular forthe extraction of strontium in low concentration, 5.10⁻⁴ M for example,from media containing 4 moles of sodium per litre.

Calixarenes with alkyl substitutes cannot therefore be used in this casesince they extract sodium more than strontium.

Moreover, the calixarenes of the invention containing 6, 7 or 8 phenylcores are more efficient than the calix[4]arenas or the calix[5]arenasfor the extraction of strontium in the presence of sodium.

To conduct extraction of strontium, in accordance with the invention,the aqueous solution containing the strontium to be separated is placedin contact with an immiscible phase containing at least one derivativeof calixarene meeting formula (I) given above, to extract the strontiumin the immiscible phase.

This immiscible phase is generally made up of a solution of thecalixarene or calixarenes of the invention in an appropriate organicsolvent.

By way of example of solvents which may be used, mention may be made ofalkyl benzenes and nitrophenyl alkyl ethers.

Preferably, an ether is used as solvent, such as ortho-nitrophenyl hexylether.

The calixarene concentration of the immiscible liquid phase depends inparticular upon the solvent used. Concentrations ranging from 10⁻⁴ to5.10⁻² mol/L may be used, for example a concentration of 10⁻² mol/L.

To implement the extraction method of the invention, the contacting ofthe aqueous solution with this immiscible liquid phase may be made inconventional liquid-liquid extraction installations, such asmixers-decanters, centrifugal extractors, pulsed columns etc.

The invention may be used to extract strontium from aqueous solutions,from nitric solutions in rparticular having a nitric acid concentrationof 1 to 4 mol/L, and to extract strontium from solutions with highsalinity, for example with sodium nitrate concentrations of 1 to 4mol/L.

It can be used in particular to extract strontium from solutions with avery low strontium concentration relative to the sodium concentration ofthese solutions.

Other characteristics and advantages of the invention will become betterapparent on reading the following example, evidently given forillustration purposes only and are non-restrictive, with reference tothe appended drawings.

SHORT DESCRIPTION OF THE DRAWINGS

FIG. 1 is a summary diagram of the calixarenes of formula (I)corresponding to examples 1 to 10.

FIG. 2 is a summary diagram of the calixarenes of formula (1)corresponding to examples 11 to 13.

FIG. 3 illustrates the changes in the coefficient of distribution D_(Sr)in relation to the nitric acid concentration of the initial solution (inmol/L) in the case of compound 10.

FIG. 4 illustrates the changes in the distribution coefficients D_(Sr)and D_(Na) and in Sr/Na selectivity in relation to the sodium nitratecontent of the initial solution (in mol/L) and for a constant HNO₃content of 1M.

FIG. 5 illustrates the changes in the distribution coefficients D_(Sr)and D_(Na) and in Sr/Na selectivity in relation to the sodium nitratecontent of the initial aqueous solution, in the absence of HNO₃, in thecase of compound 10.

DETAILED DESCRIPTION OF EMBODIMENTS

The following examples illustrate the preparation of calixarenederivatives according to the invention.

The summary diagram of examples 1 to 11 is given in FIG. 1 (compounds 1to 10).

EXAMPLE 1 Preparation of a Mixture of P-benzyloxycalix[n]arenas in Whichm Equals 6, 7 and 8

20.0 g (0.1 mol) of p-benzyloxyphenol are dissolved in 400 ml xylene ina round-bottomed 1 litre flask fitted with the water collector of DEAN &STARK type. The solution is heated to 100° C., then 1.1 ml (2 mmol) ofan aqueous 2N NaOH solution are added and 5.4 g (179.8 mmol) ofparaformaldehyde. After 2 hours, the temperature is raised to 150° C.and a precipitate starts to form. The reaction mixture is refluxed for48 hours, and it is then cooled and filtered on a Buchner funnel, whichgives a solid corresponding to the mixture of p-benzyloxycalix(nlarenesin which m equals 6, 7 and 8.

EXAMPLE 2 Preparation of5,11,17,23,29,35,41,47-octabenzyloxy-49,50,51,52,53,54,55,56-octa-hydroxycalix[8]arene(Compound 1)

The product resulting from the condensation reaction obtained in example1 is washed in diethyl ether, and it is then transferred to around-bottomed 250 ml flask and placed in suspension in 200 ml methylenechloride. The heterogeneous solution is refluxed for 3 hours, and it isthen hot filtered through a Bucher funnel. 10.2 g of a white product isobtained, formed of compound 1, i.e. a yield of 48%.

The characteristics of compound 1 are the following:

Melting point: above 300° C.; ¹H NMR (DMSO-D₆): δ=8.63 (s, 8H, OH), 7.29(s, 4OH, PhH, 6.60 (s, 16H, ArH), 4.80 (S, 16H, OCH₂Ph), 3.80 (s, 16H,ArCH₂Ar); ¹³C NMR (DMSO-D₆): δ=151.0 (s, Ar ipso), 146.6 (s, Ar para),137.6 (s, Ph), 128.9 (s, Ar ortho), 128.1 127.6 (d, Ph), 114.1 (d, ARmeta), 69.7 (t, OCH₂Ph), 32.0 (t, ArCH₂Ar); MS (CI⁻) 1696 (M⁺); Analysiscalculated for C₁₁₂H₉₆O₁₆: C, 79.23; H, 5.69. Finding: C, 79.11; H,5.80.

EXAMPLE 3 Preparation of5,11,17,23,29,35-Hexa-benzyloxy-37,38,39,40,41,42-hexahydroxycalix[6]arene (Compound 2)

The precipitation mother liquor of compound 1 obtained in example 2 isused, and the dichloromethane is removed by distilling. The residue istreated with 50 ml ethyl ether. The formed precipitate is filteredthrough a Buchner funnel. 1.1 g of compound 2 is obtained, whichcorresponds to a yield of 5%.

The characteristics of compound 2 are as follows:

Melting point: above 300° C.; ¹H NMR (DMSO-D₆, 300K); δ=8.52 (s, 6H,OH), 7.29 (m, 30H, PhH), 6.64 (s, 12H, ArH), 4.83 (s, 12H, CH₂Ph), 3.75(s, 12H, ArCH₂Ar); ¹³C NMR DMSO-D₆, 300K); δ=151.7 (s, Ar ipso), 144.9(s, Ar para), 137.2 (s, Ph), 128.6 (s, Ar ortho), 128.5, 128.1, 127.6(d, Ph), 114.3 (d, Ar meta), 69.3 (t, OCH₂Ph), 31.2 (t, ArCH₂Ar). MS(CI⁺) 1273.4 (M+H⁺); Analysis calculated for C₈₄H₇₂O₁₂: C, 79.23; H,5.69. Finding: C, 79.18; H, 5.77.

EXAMPLE 4 Preparation of5,11,17,23,29,35,41,47-Octabenzyloxy-49,50,51,52,53,54,55,56-octakis[(N,N-diethylamino-carbonyl)methoxy]calix[8]arene:(Compound 3)

The starting product is a solution containing 0.40 mmol of compound 1dissolved in 20 ml dry DMF dimethylformamide which is heated to 90° C.under stirring with Cs₂CO₃ (4 moles per each OH mole) and 6 moles foreach OH mole of α-chlorodiethylacetamide.

After 15 to 20 hours, to the cooled reaction mixture are added 75 ml 1NHCl and the crude product is filtered through a Buchner funnel andwashed in water.

The solid is dissolved in 20 ml CH₂Cl₂ and the organic solution iswashed in 2×25 ml 2N HCl and 2×25 ml water. The organic phase is driedon MgSO₄, the dichloromethane is removed by distillation and the productobtained is purified by crystallisation using CH₂Cl₂/CH₃OH at −10° C.Compound 3 is obtained with a yield of 61%.

The characteristics of compound 3 are the following:

Melting point: above 300° C.; ¹H NMR (CDCl₃); δ=7.13 (m, 40H, PhH), 6.54(s, 16H, ArH), 4.54 (s, 16H, OCH₂Ph), 4.42 (s, 16H, OCH₂CO), 4.04, (s,16H, ArHCH₂Ar), 3.25 (q, J=7 Hz, 16H, NCH₂CH₃)), 3.12 (q, J=7 Hz, 16H,NCH₂CH₃) 0.99 (t, J=7 Hz, 24H, NCH₂CH₃) 0.93 (t, J=7 Hz, 24H, NCH₂CH₃);¹³C NMR CDCl₃: δ=166.9 (s, OCH₂CO), 155.0 (s, Ar ipso), 149.2 (s, Arpara), 137.0 (s, Ph), 128.0 (s, Ar ortho), 127.5, 127.4 (d, Ph), 115.0(d, Ar meta), 72.1 (t, OCH₂CO), 69.4 (t, OCH₂Ph), 41.1, 39.9 (t,NCH₂CH₃) 30.5 (t, ArCH₂Ar), 14.1, 12.7 (q, NCH₂CH₃); MS (FAB) m/z 2601(M⁺). Analysis calculated for: C160H₁₈₄O₂₄N₈: C, 73.83; H, 7.12, N,4.30. Finding: C, 73.71; H, 7.19; N, 4.48.

EXAMPLE 5 Preparation of5,11,17,23,29,35-Hexabenzyloxy-37-38,39,40,41,41-hexakis[N,N-diethyl-aminocarbonyl)methoxy]calix[6]arene(Compound 4)

The same operating mode is followed as for example 4, to preparecompound 4 from compound 2.

The product obtained is purified by crystallization under the sameconditions and compound 4 is obtained with a yield of 75%.

The characteristics of compound 4 are as follows:

Melting point: 246-247° C.; ¹H NMR (CDCl₃, 300K): δ=7.52-7.11, 6.81,6.80, 6.19 and 5.97 (42H, PhH and ArH), 5.07-4.23 (m, 27H, OCH₂Ph,OCH₂CO, ArCH₂Ar), 3.96, 3.79, 3.40 (bs, 25H, NCH₂CH₃, ArCH₂Ar), 3.08,2.49 (q, 2H, each NCH₂CH₃), 1.86 (bs, 30H, NCH₂CH₃), 0.75 and −0.51 (t,3H each NCH₂CH₃), 0.90, 0.70, −0.19, −1.61 (bs, 1H, NCH₂CH₃); ¹H NMR(DMSO-d₆, 373K): δ=7.31 and 7.24 (s, 30H, PhH), 6.88 (bs, 12H, ArH),4.88 (s, 12H, OCH₂Ph, 4.45 (s, 12H, OCH₂CO), 3.91 (bs, 12H, ArCH₂Ar),3.26 (bs, 24H, NCH₂CH₃, 1.01 (bs 36H, NCH₂CH₃), ¹³C NMR (CDCl₃, 300K):δ=168.0, 167.6, 167.5, 167.3, 166.9 (s, OCH₂CO), 155.1, 154.9, 154.3,(s, Ar ipso), 151.4, 150.7, 148.9, (s, Ar para), 138.1, 137.6, 137.1 (s,Ph), 135.4, 134.8, 134.5, (s, Ar ortho), 133.7, 133.5, 128.5, 128.1,127.9, 127.4, 127.1, 126.9 (d, Ph), 117.4, 116.9, 116.5, 116.0, 115.3,113.8, 113.5 (d, Ar meta), 74.7, 72.5, 71.4, 70.3, 69.8, 69.2 (t,OCH₂CO), 41.62, 41.42, 41.0, 41.0, 40.1, 39.5 (t, NCH₂CH₃), 32.5, 32.1,31.1 (t, ArCH₂Ar), 14.5, 12.9, 12.3, 12.1 (q, NCH₂CH₃). Analysiscalculated for C₁₂₀H₁₃₈O₆N₁₈: C, 73.82; H, 7.12; N, 4.30. Finding: C,73.78; H, 7.18; N, 4.39. MS (CI): 1952 (M+1)⁺.

EXAMPLE 6 Preparation of 5,11, 17, 23, 29, 35, 41,47-Octahydroxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylaminocarbonyl)methoxy]calix[8]arene(Compound 5)

0.5 g of compound 3 obtained in example 4 are placed in suspension in amixture of 10 ml ethanol and 9 ml cyclohexene in a Schlenk tube undernitrogen. After adding 0.1 g (20% w/w relative to calixarene) Pd(OH)₂/C(20%, Pearlman catalyst), the reaction mixture is heated to 90° C. for15 to 18 hours. The catalyst is then removed by filtration on a Celitefilter, the filter is carefully washed with CH₂Cl₂, C₂H₅OH and againwith CH₂Cl₂.

The collected filtrates are evaporated in a vacuum to dryness, whichgives a crude product with a quantitative yield of more than 90%. Thecrude product may be crystallized using hexane and compound 5 is thusobtained with a yield of 90%.

The characteristics of compound 5 are the following:

Melting point: above 300° C.; ¹H NMR (CDCl₃/CD₃OD=3/1): δ=6.38 (s, 16H,ArH), 4.41 (s, 16H, OCH₂Ph), 3.93, (s, 16H, ArCH2Ar), 3.16 (d, J=7 Hz,16H, NCH₂CH₃, 3.13 (d, J=7 Hz, 16H, NCH₂CH₃) NCH₂CH₃) 1.04 (t, J=7 Hz,24H, NCH₂CH₃) 0.94 (t, J=7 Hz, 24H, NCH₂CH₃), ¹³C NMR (CDCl₃):CD₃OD=3:1): δ=168.7 (s, OCH₂CO), 153.9 (s, Ar ipso), 148.6 (s, Ar para),135.3 (s, Ar ortho), 116.1 (d, Ar meta), 72.0 (t, OCH₂CO), 42.1, 41.0(t, NCH₂CH₃), 30.9 (tArCH₂Ar), 14.2 12.9 (q, NCH₂CH₃), MS (FAB⁺) m/z1880.7 (M⁺); Analysis calculated for C₁₀₄H₁₃₆O₂₄N₈: C, 66.37; H, 7.27;N; 5.95. Finding: C, 66.45; H, 7.39; N, 6.07.

EXAMPLE 7 Preparation of5,11,17,23,29,35-Hexahydroxy-37,38,39,40,41,42-hexakis[N,N-diethylaminocarbonyl)-methoxy]calix[6]arene(Compound 6)

In this example, the same operating mode is followed as in example 6 toprepare compound 6 from compound 4.

Compound 6 is obtained with a yield of 80%.

The characteristics of compound 6 are the following:

Melting point: 255° C. (decomposed); ¹H NMR (DMSO-d₆, 300K): δ=8.3 (bs,6H, ArOH), 6.6 (bs, 12H, ArH), 4.21 (bs, 12H, OCH₂CO), 3.85 (bs, 12H,ArCH₂Ar) 3.30 (bs, 24H, NCH₂CH₃), 1.0 (bs, 36H, NCH₂CH₃), ¹H NMR(DMSO-d₆, 343K); δ=8.11 (s, 6H, ArOH), 6.35 (s, 12H, ArH), 4.35 (s, 12H,OCH₂CO), 3.81, (s, 12H, ArCH₂Ar) 3.20 (bs, 24H, NCH₂CH₃), 0.90 (bs, 36H,NCH₂CH₃), ¹³C NMR (CDCl₃): d=166.8 (s, OCH₂CO), 152.5 (s, Ar ipso),147.8 (s, Ar para), 113.6 (s, Ar ortho), 115.8 (d, Ar meta), 79.4 (t,OCH₂CO), 40.71 (t, NCH₂CH₃), 30.3 (t, ArCH₂Ar), 13.7, 12.6 (q, NCH₂CH₃),MS (FAB+) m/z 1410.9 (M⁺). Analysis calculated for C₇₈H₁₀₂O₆N₁₈: C,66.36; H, 7.28; N, 5.95. Finding: C, 66.44; H, 7.33; N, 6.02.

EXAMPLE 8 Preparation of5,11,17,23,29,35-Hexamethoxy-37,38,39,40,41,42-hexakis[N,N-diethylaminocarbonyl)-methoxy]calyx[6]arene(Compound 7)

To a stirred solution of 0.5 mmol of compound 6 dissolved in 80 ml dryDMF are added 3 moles Cs₂CO₃ for each OH mole and iodomethane to theproportion of 3 mol per OH mole. The reaction mixture is heated to 90°C., in a nitrogen atmosphere, for 18 hours. The DMF is then removedunder reduced pressure and the residue is cooled with 75 ml 10% HClaqueous solution. 75 ml dichloromethane are added, the organic layer isseparated and washed twice in 50 ml water. The organic phase is dried onMgSO₄ and the solvent is removed under reduced pressure.

Compound 7 is obtained with a yield of 95%.

The characteristics of compound 7 are the following:

Melting point: 108-110° C.; ¹H NMR (DMSO-D₆, 300K): δ=7.3-6.8 and 5.7(bs, 12H, ArH), 4.63 (bs, 12H, OCH₂CO), 4.3 (bs, 12H, ArCH₂Ar), 3.9-3.4(bs, 42H, OCH₃ and NCH₂CH₃), 1.10 (bs, 36H, NCH₂CH₃), ¹H NMR (DMSO-d₆,343K): d=6.70 (s, 12H, ArH), 4.43 (s, 12H, OCH₂CO), 3.85 (s, 12H,ArCH₂Ar), 3.54 (s, 18H, OCH₃), 3.17 (bs, 24H, NCH₂CH₃), 0.96 (bs, 36H,NCH₂CH₃); ¹³C NMR (CDCl₃, 300K): δ=167.1, 166.7 (s, OCH₂CO), 155.9,155.8 (s, Ar ipso), 148.5, 148.3 (s, Ar para), 136.2, 135.3, 135.1,134.5, 134.2 (s, Ar ortho), 116.6, 116.0, 115.7, 114.8, 114.6, 113.9 (d,Ar meta), 72.4, 72.2 (t, OCH₂CO), 57.4, 56.8, 55.3 (q, OCH₃), 41.2, 39.9(t, NCH₂CH₃), 31.7 (t, ArCH₂Ar), 14.5, 12.8 (q, NCH₂CH₃). Analysiscalculated for C₈₄H₁₁₄N₆O₁₈: C, 67.44; H, 7.68; N, 5.62. Finding: C,67.38; H, 7.75; N, 5.73. MS (CI+)=1496 (M+H⁺).

EXAMPLE 9 Preparation of5,11,17,23,29,35,41,47-Octamethoxy-49,50,51,52,53,54,55,56-octakis[(N,N-diethylaminocarbonyl)methoxy]calix[8]arene(Compound 8)

The same operating mode is followed as for example 8 to prepare compound8 from compound 5 also using iodomethane CH₃I.

Compound 8 is obtained with a yield of 70%.

The characteristics of this compound are as follows:

Melting point: 96-97° C.; ¹H NMR CDCl₃: δ=6.43 (s, 16H, ArH), 4.43 (s,16H, OCH₂CO), 4.04 (s, 16H, ArCH₂Ar), 3.45 (s, 24H, OCH₃) 3.29 (d, 16H,NCH₂CH₃), J=6.3 Hz), 3.13 (d, 16H, NCH₂CH₃), J=6.3 Hz), 1.04 (t, 24H,NCH₂CH₃), J=6 Hz), 0.90 (t, 24H, NCH₂CH₃ J=6 Hz). ¹³C NMR (CDCl₃, 300K):δ=166.9 (s, OCH₂CO), 155.9, (s, Ar ipso), 148.9 (s, Ar para), 134.6 (s,Ar ortho), 113.9 (d, Ar meta), 72.0 (t, OCH₂CO), 54.9 (s, OCH₃), 41.0,39.8 (t, NCH₂CH₃) 30.5 (t, ArCH₂Ar), 14.0, 12.6 (q, NCH₂CH₃). Analysiscalculated for C₁₁₂H₁₅₂N₈O₂₄: C, 67.45; H, 7.68; N, 5.62. Finding: C,67.54; H, 7.56; N, 5.77. MS (CI+): m/z=1994 (M+H⁺).

EXAMPLE 10 Preparation of5,11,17,23,29,35,41,47-Octapentoxy-49,50,51,52,53,54,55,56-ocatkis[N,N-diethylaminocarbonyl)methoxy]calix[8]arene(Compound 9)

The same operating mode is followed as for example 8 to prepare compound9 from compound 5, using n—CH₃(CH₂)₄I as alkylation agent.

Pure compound 9 is obtained by flash chromatography (SiO₂:AcOEt/MeOH=10/1) with a yield of 65%.

The characteristics of this compound are as follows: ¹H NMR CDCl₃:δ=6.49 (s, 16H, ArH), 4.37 (s, 16H, OCH₂CO), 4.00 (s, 16H, ArCH₂Ar),3.65 (bs, 16H, OCH₂R) 3.24 (bs, 16H, NCH₂CH₃), 3.11 (bs, 16H, NCH₂CH₃),1.55 (bs, 48H, (CH₂)₃), 1.28 (bs, 24H, RCH₃), 1.01 (t, 24H, NCH₂CH₃,0.85 (t, 24H, NCH₂CH₃). ¹³C NMR (CDCl₃): δ=166.9 (s, OCH₂CO), 155.3, (s,Ar ipso), 148.9 (s, Ar para), 134.3 (s, Ar ortho), 114.6 (d, Ar meta),72.1 (t, OCH₂CO), 67.7 (s, OCH₂R), 41.0, 39.8 (t, NCH₂CH₃) 30.4 (t,ArCH₂Ar), 28.8 (t, CH₂CH₂CH₂CH₃), 28.7 (t, CH₂CH₂CH₃), 22.3 (t, CH₂CH₃),13.8 (q, CH₃), 14.0, 12.6 (q, NCH₂CH₃). Analysis calculated forC₁₄₄H₂₁₆N₈O₂₄: C, 70.79; H, 8.91; N, 4.59. Finding: C, 70.83; H, 8.86;N, 4.66. MS (CI+): m/z=2443 (M+H)⁺.

EXAMPLE 11 Preparation of5,11,17,23,29,35,41,47-Octaoctoxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylaminocarbonyl)methoxy]calix[8]arene(Compound 10)

In this example the same operating mode is followed as in example 8using compound 5 and using n—CH₂3(CH₂)₇ Ots as alkylation agent.

Compound 10 is obtained in the pure state by flash chromatography (SiO₂:AcOEt/MeOH=10/0.1), with a yield of 57%.

The characteristics of compound 10 are the following.

Melting point: 68-70° C.; ¹H NMR CDCl₃: δ=6.47 (bs, 16H, ArH), 4.34 (bs,16H, OCH₂CO), 3.99 (s, 16H, ArCH₂Ar), 3.65 (bs, 16H, OCH₂R) 3.22 (bs,32H, NCH₂CH₃), 1.23 (bs, 96H, (CH₂)₆CH₃), 0.90 (bs, 24H, NCH₂CH₃), 0.86(bs, 24H, NCH₂CH₃), 0.83 (t, J=6.5 Hz, 24H, (CH₂)₇CH₃). 13C NMR (CDCl₃):δ=166.9 (s, OCH₂CO), 155.2, (s, Ar ipso), 148.9 (s, Ar para), 134.4 (s,Ar ortho), 114.6 (d, Ar meta), 72.0 (t, OCH₂CO), 67.7 (s, OCH₂R), 41.0,39.8 (t, NCH₂CH₃) 31.7 (t, CH₂CH₂CH₂CH₂CH₂CH₃) 30.4 (t, ArCH₂Ar), 29.5(t, CH₂CH₂CH₂CH₂CH₃), 22.4 (t, CH₂CH₃) 13.8 (q, CH₃), 14.0, 12.6 (q,NCH₂CH₃). Analysis calculated for C₁₆₈H₂₆₄N₈O₂₄: C, 72.58; H, 9.57; N,4.03. Finding: C, 72.62; H, 9.51; N, 4.12. MS (CI+): m/z=27779 (M+1)⁺.

The summary diagram of examples 12 to 14 is illustrated in FIG. 2.

EXAMPLE 12 Preparation of 5,11,17,23,29,35,41,47-Octakis(1,1-dimethylethyl)-49,50,51,52,53,54,55,56-octakis[N,N-diethylaminocarbonyl)methoxy]calix[8]arene (Compound 11)

In this example, the same operating mode is followed as in example 4 toprepare compound 11 from5,11,17,23,29,35,41,47-octakis(1,1-dimethylethyl)calyx [8]arene, that isto say the compound of formula (III) in which R represents thetert-butyl group and m equals 8.

Compound 11 is thus obtained in the pure state by crystallization usingmethanol, with a yield of 64%.

The characteristics of compound 11 are as follows:

Melting point: above 300° C.; ¹H NMR CDCl₃: δ=6.69 (bs, 16H, ArH), 4.37(s, 16H, OCH₂CO), 4.13 (s, 16H, ArCH₂Ar), 3.21 (bs, 16H, NCH₂CH₃) 1.05(s, 72H, tBu), 1.22 (t, 24H, J=7 Hz, NCH₂CH₃), 0.84 (t, 24H, J=7 Hz,NCH₂CH₃). ¹³C NMR (CDCl₃): δ=167.0 (s, OCH₂CO), 153.4 (s, Ar ipso),146.0 (s, Ar para), 132.5 (s, Ar ortho), 125.9 (d, Ar meta), 71.1 (t,OCH₂CO), 41.1, 39.9 (t, NCH₂CH₃) 34.1 (s, C(CH₃)₃), 31.2 (t, ArCH₂Ar),31.4 (s, C(CH₃)₃), 14.0, 12.8 (q, NCH₂CH₃). Analysis calculated forC₁₃₆H₂₀₀N₈O₁₆: C, 74.14; H, 9.15; N, 5.09. Finding: C, 74.03; H, 9.22;N, 5.18. MS (CI+)=2201 (M⁺).

EXAMPLE Preparation of49,50,51,52,53,54,55,56-Octakis[N,N-diethylaminocarbonyl)methoxy]calix[8]arene(Compound 12)

The same operating mode is followed as in example 4 to prepare compound12 from calix[8]arene. The pure compound 12 is obtained by flashchromatography (SiO₂, AcOEt/MET₃=10/0.5) and crystallization using coldethyl acetate, with a yield of 75%.

The characteristics of compound 12 are the following:

Melting point: 84-86° C.; ¹H NMR CDCl₃: δ=6.61 (bs, 16H, ArH), 4.40 (s,16H, OCH₂CO), 4.10 (s, 16H, ArCH₂Ar), 3.31-3.01 (m, 32H, NCH₂CH₃),1.10-0.77 (m, 48H, NCH₂CH₃), ¹³C NMR (CDCl₃): δ=166.8 (s, OCH₂CO), 155.4(s, Ar ipso), 133.8 (s, Ar ortho), 129.0 (d, Ar meta), 124.3 (d, Arpara), 71.5 (t, OCH₂CO), 40.9, 39.7 (t, NCH₂CH₃) 30.4 (t, ArCH₂Ar),13.9, 12.7 (q, NCH₂CH₃). Analysis calculated for C₁₀₄H₁₃₆N₈O₁₆: C,71.20; H, 7.81; N, 6.39. Finding: C, 71.15; H, 7.79; N, 6.44. MS(CI)=1753 (M)⁺.

EXAMPLE 14 Preparation of5,11,17,23,29,35,41-Heptakis(1,1-dimethylethyl)-43,44,45,46,47,48,49-heptakis[N,N-diethylaminocarbonyl)methoxy]calix[7]arene(Compound 13)

Compound 13 is obtained following the same operating mode as in example4 using 5,11,17,23,29,35,41-heptakis(1,1-dimethylethyl)calix[7]arene.

This calixarene was prepared using the method described by Shinkai,Bull. Chem. Soc. Jpn, 1994, 10499 [3]; Markoxitz JACS, 1989, 111, 81-92[4].

Compound 13 is obtained in the pure state by crystallization usingmethanol, with a yield of 70%.

The characteristics of this compound are the following:

Melting point: above 248-250° C. ¹H NMR CDCl₃: δ=7.03 (s, 14H, ArH),4.48 (s, 14H, OCH₂CO), 4.04 (s, 14H, ArCH₂Ar), 3.38-3.23 (m, 28H,NCH₂CH₃) 1.03 (s, 63H, tBu), 1.00 (t, 42H, J=7 Hz, NCH₂CH₃). ¹³C NMR(CDCl₃): δ=167.2 (s, OCH₂CO), 153.4 (s, Ar ipso), 147.1 (s, Ar para),132.6 (s, Ar ortho), 126.4 (d, Ar meta), 72.1 (t, OCH₂CO), 40.1, 39.9(t, NCH₂CH₃) 34.0 (s, C(CH₃)₃), 31.4 (s, C(CH₃)₃), 31.2 (t, ArCH₂Ar),14.5, 12.9 (q, NCH₂CH₃). Analysis calculated for C₁₁₉H₁₇₅N₇O₁₄: C,74.14; H, 9.15; N, 5.09. Finding: C, 74.07; H, 9.20; N, 5.13. MS (CI+):1926.8 (M⁺).

EXAMPLE 15

In this example, the efficacy of the compounds of the invention istested to extract the following M metals: caesium-137, strontium-85 andsodium-22, from an aqueous nitric solution having a nitric acidconcentration of 1M and containing 5.10⁻⁴ M of metals M to be extracted.

In this example, 3 ml of each aqueous solution containing only one ofthe metals to be extracted is contacted with 3 ml of an organic solutionmade up of nitrophenyl hexylether (NPHE) containing 10⁻² mol/L of thetested calixarene. Contact is made in a 20 ml polypropylene tube whichis shaken.

After a contact time of 1 hour, the two phases are left to settle andtheir respective contents of sodium, strontium and caesium are measured.

The distribution coefficient D_(M) is then determined corresponding tothe ratio of the concentration of element M in the organic phase overthe concentration of this same element M in the aqueous phase.

The results obtained and the tested calixarenes are given in table 1.

EXAMPLE 16

In this example, the extracting properties of the calixarenes of theinvention are tested vis-à-vis cobalt-60, strontium-85, caesium-137 andeuropium-152 present in an aqueous solution containing 10⁻² mol/L HNO₃and 4 mol/L NaNO₃. The same operating mode is followed as in example 15to assure extraction of the compounds listed in table 2 whoseconcentration in NPHE is 10⁻² mol/L.

The results obtained are given in table 2.

EXAMPLE 17

In this example, the efficacy of the calixarenes of the invention istested to extract ⁶⁰Co, ⁸⁵Sr, ¹³⁷Cs and 152Eu from an aqueous solutionhaving a nitric acid concentration of 1 mol/L and containing 4 mol/LNaNO₃.

The operating mode is identical to the one in example 15, and theresults obtained and the calixarenes used are given in table 3.

EXAMPLE 18

In this example, the efficacy of the calixarene (compound 10) is testedto extract strontium from nitric aqueous solutions having variableconcentrations (10⁻³, 10⁻², 10⁻¹, and 10 M) in nitric acid.

The same operating mode is followed as in example 15 with compound 10 ata concentration of 10⁻² mol/L in NPHE.

The results obtained are given in FIG. 3 which illustrates the changesin the distribution coefficient D_(Sr) in relation to the nitric acidconcentration.

EXAMPLE 19

In this example, the efficacy of the calixarene (compound 10) is testedto extract strontium and sodium from aqueous solutions with a nitricacid concentration of 1 M and variable NO₃Na concentrations (0.5, 1, 2,3 and 4 M). The same operating mode is followed as in example 15 usingan organic phase made up of compound 10 at a concentration of 10⁻² mol/Lin NPHE.

The results obtained are given in FIG. 4 which illustrates the changesin D_(Sr), D_(Na) and Sr/Na selectivity in relation to the concentrationof NaNO₃.

EXAMPLE 20

In this example, the efficacy of the calixarene (compound 10) is testedto extract strontium and sodium from aqueous solutions without nitricacid having variable NO₃Na concentrations (0.5, 1, 2, 4 and 4 M). Thesame operating mode is followed as in example 15 using an organic phasemade up of compound 10 at a concentration of 10⁻² mol/L in NPHE.

The results obtained are given in FIG. 5 which illustrates the changesin D_(Sr), D_(Na) and Sr/Na selectivity in relation to the concentrationof NaNO₃.

CITED REFERENCES

[1] WO94/12502.

[2] WO94/24138.

[3] Shinkai, Bull. Chem. Soc. Jpn., 1994, 10499.

[4] Markoxitz JACS, 1989, 111, 81-92.

TABLE 1 Example 15 Calixarene in M(NO₃)n 5.10⁻⁴ M—HNO₃ 1M NPHE 10⁻² M ²²Na ⁸⁵Sr ¹³⁷Cs Sr/Na Compound 3 <10⁻³ 20 <10⁻³ >20000 Compound 8 <10⁻³6.5 <10⁻³ 6500 Compound 9 <10⁻³ 30 <10⁻³ >30000 Compound 10 <10⁻³ 24<10⁻³ >24000 Compound 11 Precipitation Compound 12 6.10⁻³ 8.3 10⁻² 1400Compound 4 <10⁻³ 2.9 <10⁻³ >2900 Compound 13 0.04 1.13 28

TABLE 2 Example 16 Calixarene in NaNO₃ 4M - HNO₃ 10⁻² M NPHE 10⁻² M ²²Co⁸⁵Sr ¹³⁷Cs ¹⁵²Eu Compound 3 <10⁻³ 1.5 6.10⁻² <10⁻³ Compound 8 <10⁻³ 0.8<10⁻³ <10⁻³ Compound 9 <10⁻³ 1.5 <10⁻³ 4.10⁻² Compound 10 <10⁻³ 1.39.10⁻³ 9.10⁻² Compound 11 <10⁻³ 8.10⁻² 1,6.10⁻² <10⁻³ Compound 12 <10⁻³0.5 3.10⁻³ <10⁻³

TABLE 3 Example 17 Calixarene in NaNO₃ 4M - HNO₃ 1M NPHE 10⁻² M ⁶⁰Co⁸⁵Sr ¹³⁷ _(Cs) ¹⁵²Eu Compound 3 <10⁻³ 5 0.1 <10⁻³ Compound 8 <10⁻³ 2.20.28 <10⁻³ Compound 9 <10⁻³ 0.34 0.14 <10⁻³ Compound 10 <10⁻³ 3.8 0.27<10⁻³ Compound 11 <10⁻³ 0.4 0.2 <10⁻³ Compound 12 <10⁻³ 1.3 3.10⁻² <10⁻³Compound 4 <10⁻³ 1.8 <10⁻³ <10⁻³ Compound 13 0.13

What is claimed is:
 1. Derivative of calixarene having the formula:

in which: R¹ represents a hydroxyl, alcoxy, aryloxy, arylalcoxy, orcycloalcoxy group, or a group having the formula O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴ represents a hydrogen atom or analkyl group, n and p are whole numbers ranging from 1 to 6, and q equals0 or is a whole number from 1 to 6, R² and R³, which identicaldifferent, represent an alkyl, cycloalkyl or aryl group or a grouphaving the formula: O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴, n, pand q are such as defined above, or R² and R³, together with thenitrogen atom to which they are bound, form a heterocyclic group chosenfrom among the piperidyl, pyrrolidinyl, morpholinyl, thiomorpholinyl,tetrahydropyridyl, imidazolidinyl, indolinyl, tetrahydroquinolyl andperhydroindolyl groups, and m is a whole number ranging from 6 to
 8. 2.Calixarene derivative according to claim 1, in which R¹ is an alcoxy orarylalcoxy group.
 3. Calixarene derivative according to claim 2, inwhich the alcoxy group is the pentoxy or octoxy group.
 4. Calixarenederivative according to claim 2, in which the arylalcoxy group is thebenzyloxy group.
 5. Calixarene derivative according to claim 1, in whichR² and R³ are alkyl groups.
 6. Calixarene derivative according to claim1, in which m equals 6 or
 8. 7. Calixarene derivative chosen from among:5,11,17,23,29,35,41,47-octabenzyloxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35,41,47-octamethoxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35-hexamethoxy-37,38,39,40,41,42-hexakis[N,N-diethylaminocarbonyl)methoxy]-calix[6]arene,5,11,17,23,29,35-hexabenzyloxy-37,38,39,40,41,42-hexakis[N,N-diethylamino-carbonyl)methoxy]calix[6]arene,5,11,17,23,29,35,41,47-octakis(1,1-dimethylethyl)-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35,41,47-octapentoxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35,41,47-octaoctoxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35,41,47-octahydroxy-49,50,51,52,53,54,55,56-octakis[N,N-diethylamino-carbonyl)methoxy]calix[8]arene,5,11,17,23,29,35,41-heptakis(1,1-dimethylethyl)-43,44,45,46,47,48,49-heptakis(N,N-diethylamino-carbonyl)methoxy]calix[8]arene, and5,11,17,23,29,35-hexahydroxy-37,38,39,40,41,42-hexakis[N,N-diethylaminocarbonyl)methoxy]calix(6]arene.
 8. Method for preparinga calixarene derivative having the formula:

in which: R¹ represents a hydrogen atom, an alkyl group or a benzyloxygroup, R² and R³, which may identical or different, represent an alkyl,cycloalkyl or aryl group or a group having the formula:O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴, n, p and q are such asdefined above, or R² and R³, together with the nitrogen atom to whichthey are bound, form a heterocyclic group chosen from among thepiperidyl, pyrrolidinyl, morpholinyl, thiomorpholinyl,tetrahydropyridyl, imidazolidinyl, indolinyl, tetrahydroquinolyl andperhydroindolyl groups, and m is a whole number ranging from 6 to 8,which comprises the reaction of a calixarene having the formula:

 in which R¹ and m are such as defined above, with a chloroacetamidehaving the formula:

in which R² and R³ are such as defined above.
 9. Method for preparing acalixarene derivative having the formula:

in which: R¹ represents an alcoxy group, R² and R³, which may identicalor different, represent an alkyl, cycloalkyl or aryl group or a grouphaving the formula: O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴, n, pand q are such as defined above, or R² and R³, together with thenitrogen atom to which they are bound, form a heterocyclic group chosenfrom among the piperidyl, pyrrolidinyl, morpholinyl, thiomorpholinyl,tetrahydropyridyl, imidazolidinyl, indolinyl, tetrahydroquinolyl andperhydroindolyl groups, and m is a whole number ranging from 6 to 8,which comprises the following steps: a) reaction of a calixarene havingthe formula:

 in which m is such as defined above, with a chloroacetamide having theformula:

 in which R² and R³ are such as defined above, in order to obtain thederivative having the formula:

 in which R² and R³ are such as defined above, b) reaction of thederivative of formula (VI) with Pd(OH₂) to obtain the calixarene havingthe formula:

c) reaction of the calixarene of formula VII with a halogenatedderivative of formula R⁵X in which R ⁵ represents an alkyl group and Xis a halogen atom, to obtain the calixarene derivative of formula (I) inwhich R¹ represents the alcoxy group OR⁵.
 10. Met hod for preparing acalixarene derivative having the formula:

in which R¹ represents the benzyloxy group and m equals 6 or 8, bycondensation reaction of p-benzyloxyphenol having the formula:

to obtain a mixture of calix[6]arene, calix[7]arene and calix[8]arene offormula (III), and separation of the calixarene of formula (III) inwhich m=6 or
 8. 11. Method for extracting strontium present in anaqueous solution, which consists of contacting the aqueous solution withan immiscible phase containing at least one calixarene derivative havingthe formula:

in which: R¹ represent a hydrogen atom, an alkyl, alcoxy, aryl, aryloxy,arylalkyl, arylalcoxy, cycloalkyl or cycloalcoxy group, or a grouphaving the formula: O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴represents a hydrogen atom or an alkyl group, n and p are whole numbersranging from 1 to 6, and q equals 0 or is a whole number from 1 to 6, R²and R³, which may identical or different, 5 represent an alkyl,cycloalkyl or aryl a group having the formula:O(CH₂)_(n)[O(CH₂)_(p)]_(q)OR⁴ (II) in which R⁴, n, p and q are such asdefined above, or R² and R³, together with the nitrogen atom to whichthey are bound, form a heterocyclic group chosen from among thepiperidyl, pyrrolidinyl, morpholinyl, thiomorpholinyl,tetrahydropyridyl, imidazolidinyl, indolinyl, tetrahydroquinolyl andperhydroindolyl groups, and m is a whole number ranging from 6 to 8, toextract strontium in the immiscible phase.
 12. Method according to claim11, in which the aqueous solution is a nitric solution containing from 1to 4 mol/l nitric acid, or a saline solution having a sodium nitrateconcentration of 1 to 4 mol/L.
 13. Method according to claim 11, inwhich the immiscible phase is a solution of the derivative of calixareneof formula (I) in an organic solvent.
 14. Method according to claim 13,in which the organic solvent is a nitrophenyl-alkylether.